The demand for short linear alpha olefins is constantly increasing and motivates the development of robust and selective catalysts.In
this thesis, several libraries of phosphorus ligands with the capacity to form dissymmetric or supramolecular assemblies were
synthesized. The variability observed within the aminophosphine libraries, clearly reflected by the various tautomeric equilibrium
of the ligand, was also observed in the nickel complexes as a single ligand could generate several complexes with different
structures.Sulphonyliminobisphosphine were then introduced as a new class of ligands. These precursors rearrange in the
presence of nickel to generate diphosphinamine nickel complexes. Activated by MAO, these complexes are active in the reaction
of ethylene oligomerisation and produce short chain olefins.A new approach that forms stable supramolecular nickel complexes
was developed by combining two phosphorus ligands with Ni(0). These complexes stabilised by hydrogen bonding are directly
active in the reaction of ethylene oligomerisation with some catalysts leading to high selectivity to 1‐butene (up to 84%).
To understand the origin of that selectivity, the scope of complexes was extended to ligands with different steric and electronic
properties. Their evaluation in the reaction of ethylene oligomerisation evidenced a relation between the catalyst structure
and the selectivity of the reaction. Mechanistic studies, under an ethylene atmosphere, reveals that cationic complexes rearrange
to neutral complexes, which are likely, the active species.

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